Light-sensitive silver halide photographic material sensitized with a thiohydantoin nucleus containing dye

ABSTRACT

THE PHOTOGRAPHIC MATERIAL EMULSION LAYER CONTAINS A SENSITIZING DYE. THE DYE HAS THE FORMULA:   1-(R1-(CH2)N-,2-(S=),3-R2,4-(O=),5-((-N(-R)-Z-)&gt;C=CH-CH=)   IMIDAZOLIDINE   WHERIN R IS AN ALKYL GROUP, A CARBOXY ALKYL GROUP OR A SULFO ALKYL GROUP; R1 IS HYDROXY, CYANO, ALKOXY, CARBOXY, ACYLOXY OR CARBAMOYL; N IS A INTEGER OF 2 TO 3; R2 IS A SUBSTITUTED OR UNSUBSTITUTED ALKYL, ARYL, ALKENYL OR ARALKYL; AND Z MEANS AN ATOMIC GROUPING CAPABLE OF FORMING, TOGETHER WITH THE ADJACENT NITROGEN AND CARBON ATOMS, A BENZOXAZOLE RING, A NAPHTHO-OXAZOLE RING, A THIAZOLE RING, AND INDOLENINE RING OR A QUINOLINE RING.

Dec. 7, 1971 SPECTRAL KAIlCHlRO SAKAZUME ETAL 3,625,698 LIGHT-SENSITIVESILVER HALIDIS PHOTOGRAPHIC MATERIAL SENSITIZED WITH A THIOHYDANTOINNUCLEUS CONTAINING DYE Filed June 14, 1968 JE g; F/G. 5 a LU 2 Q. LLI mU) l l l 350 400 450 500 550 600 -W/-\VE LENGTH E E F/G.2 U (D Z O. I-LlU) (I) I [I l I 1 l 350 400 450 500 550 600 WAVE LENGTH g z 3 U (D LLI ZO. LLI (D (J7 WAVE LENGTH KAIICHIRO SAKAZUME SHIGEMASA ITOH SHUI SATO A'EIICHI SAKAMOTO 350 400 450 500 550 600 INVI'JNIHHS WAVE LENGTH HY WWV- BMW A'I'TORNI'JYS United States Patent 3 625 698 LIGHT-SENSITIVEsILvER HALIDE PHOTO- GRAPHIC MATERIAL SENSITIZED WITH A "ice newpolymethine-merocyanine dye having a thiohydantoin nucleus, said dyebeing a new compound of the general formula (CH n R1 THIOHYDANTOINNUCLEUS CONTAINING 5 -z D YE O=CHOH=C-N Kalichlro Sakazume, ShIgemasaItoh, and Shur Sato,

Tokyo, and Eiichi Sakamoto, Hanno-shi, Japan, as- {i O: signors toKonishiroku Photo Industry Co., Ltd. 0=c- N Filed June 14, 1968, Ser.No. 737,147 1 Claims priority, application Japan, June 20, 1967, 1

42/259,037; Aug. 25, 1967, 42/54,205

Int. Cl. G03c 1/08 wherein -R is unsubstituted or substituted alkyl; Ris US. Cl. 96-100 5 Claims hydroxy, cyano, alkoxy, carboxy, acyloxy orcarbamoyl;

n is an integer of 2 to 3; R is unsubstituted or substituted alkyl,aryl, alkenyl or aralkyl; and Z means an ABSTRACT OF THE DISCLOSUREatomic grouping capable of forming, together with the The photographicmaterial emulsion layer contains a adjacent i g and carbon atoms, a6-membeled sensitizing dye. The dye has the formula: heterocychcnucleus, this heterocyclic nucleus being able (CHQFR! to contain asubstituent. Various sensitizing dyes have been known in the photo- Egraphic art. Some of them are excellent in sensitizing -N c=s action buttend to cause an increase of fog. Further, al-

0: most all of the known sensitizing dyes sufier from the decrease ofsensitiveness during the storage of the film R1 product. wherein R is analkyl group, a carboxy alkyl group or It is accordingly an object of thepresent invention a sulfo alkyl group; R is hydroxy, cyano, alkoxy,carto provide a new sensitizing dye having well balanced boxy, acyloxyor carbamoyl; n is an integer of 2 to 3; properties useful forphotography. It has now been found R is a substituted or unsubstitutedalkyl, aryl, alkenyl that a new polymethine merocyanine dye having aparor aralkyl; and Z means an atomic grouping capable of ticularthiohydantoin nucleus when it is incorporated forming, together with theadjacent nitrogen and carbon in the photographic emulsion layer of aphotographic atoms, a benzoxazole ring, a naphtho-oxazole ring, amaterial is entirely free from the decrease of photographic thiazolering, and indolenine ring or a quinoline ring. sensitivity during thestorage of the photographic material and safe from color staining of thephotographic emulsion layer after development, while it exhibits goodThis invention relates to a light-sensitive silver halide sensitizingeffect. photographic material, characterized by that it contains, Beloware typical compounds of the general formula as an ingredient for itsphotographic emulsion layer, a used in this invention.

/'Z i C=OHCH=C-N l? /C=S (R =(CH1)nR]) R 0=GI;I

"'Z\ Comi o Mem n X)m(nix. n l -N R R2 R dbl) Egon;

(1) O CzH5 -CH2CH2OH 278-281 492 (2) Same as above. CH3 01 Same as above277-279 496 a ..do -oiHi oH2oH,ococH, 1 250-252 492 (4) /O -CH CHiCOOHSame as above; CHiCH2OH 235-238 493 TABLEContinued Oom- E C Melting 7\max. pound 2 point (11111) (in N o. "N R R: R C.) MeOH) (5) 0 -O2H5CHzCH2CHa Same as above 206-208 502 CH3O f N v (6) O\- -CHzOHzCOOH I 6d0 233-235 490 (7) O OZH5 CHzCH2GH3 ...--d0 250-252 496 (8) Same asabove Same as above Same as above -CHZCHZOCOCH 182-185 495 (9) O do CHzCHzOH 265-267 505 CHsO- (10) O CHzCHzC/00H Same as above Same as above225-227 496 Y G: CHaO- N (11) Same as above --C2 5 01 d0 250-253 499(12) O CHzCHzCOOH Same as above do 246-248 490 (13) Same as above Sameassabove CHzCH2CH3 do 221-223 487 (14) O --C2H5 -d0 236289 501 (15) Sameas above Same as above C1 .do 17727u 501 \0 (RH: CHzSO HN H N (17) /O$11: Same as abov'e d0 I' 242-245 496 C: I O N CHZSOQHN H (18) -G2H5 dod0 222-225 635 (19) /S\ CH; (10 -OHzOHzOCOGH 1 285-287 528lABLE00ntinued |-Z\ Com-d c Mem A poun po m n N0. -N R R: R C.) MeOH)(20) Same as above O;H ...-d0 CH2CH2OH 260262 526 (21) 0 Same as above.-do -CH2GHzCH2OH 223-225 500 (22) CH CH3 --CH; ..d0 CHOH2OH 193-196 498(23) C2H5 ..d0 Same as above 293-295 508 (24) O\ Same as above .do-OH2CH2GH2OOH(OH 220-223 497 (25) Same as above -OH2OH2OO0H -do-CHzCH2OCH(CH3)z 235-238 490 (26) O C2H5 ...--do CH:CH:OH2OCH3 211-214500 (27) 0 Same as above Same as above 237-240 405 (28) O -..--d0CH:CHzCN 242-244 501 C: CHaO- (29) Same as above d0 G01 Same as above276-278 501 fin -CHzCHzCH 210-212 496 (31) 0 --CH Same as above ..do274-276 488 (32) O -C2H5 -CH2CH= CH1 do 212-214 495 (33) O\ --CHzCHzC 0OH .-..d0 248-251 490 TABLE-Continued Z Com-d Melting linzix. oun poinmy 11 N0. "N R R2 R C.) MeOH) (35) H; S\ Same as above 6 do 223226 480C: H2 '-N (36) O CH, Same as above do 251-252 495 cmo- E 0: I E C N SO3HN H (37) N/ C:Hs CH2C1I=CH: CH2CH;CN 17(1-172 624 (38) 0 Same asabove CH2OHC 0 OH 277-279 495 (39) 0 ....-do Same as above. Sameas above295298 500 c: omo- 40 0 7 .....do ..do --do 2%299 495 .....do .-d0 do278-281 500 C: CHa- (43) 0 .....do Sameas above.....; ..d0 283285 493 44v 0 ...-.do -.CH;CH=OH do 262-265 493 C: GHaO- (45) 0 do .-do 298-299508 (46) Same as above ..d0 n .-do 261-264 507 (47) 0 ---..d0-C.HzCHnCHa d0 266-269 493 TABLEOontinued Oomi C Melting hm. pound point(my) (in No. N R 2 R C C.) MeOH) (48) /O\ d d0 293-296 530 H -S .do-Cl'l2(llz llx -do 237-240 475 (60) /O .rlo C1 -ClIOHzCONl-l 300 405(51) 0 .do Same asabove Same as above 300 503 c: omo- (52) 0 doCH2CH2CHa (lo 279-282 480 53 o\ .do -CHZCH=CHQ Mao 241-243 49 l orno-(55) Same as above .do do 300 492 1 Decomposition.

Now, the preparation of some of the aforementioned compounds isexemplified below.

Synthesis of compound 3 in 110 ml. of water and the resulting solutionis refluxed for 3 hours and then cooled to room temperature. 47 m1. ofconcentrated hydrochloric acid is added to the solution and reflux iscarried out for further 2 hours. Methanol is distilled off under reducedpressure. A crystal is formed by adding water and cooling. The crystalis filtered and Washed with a little alcohol-ether to give 38 g. ofcrude crystal. Recrystallization from 160 ml. of alcohol yields 20 g. of1-hydroxyethy1-3-phenyl 2 thiohydantoin as white flocculent crystal. 0.7g. of the 1-hydroxyethyl-3- phenyl-Z-thiohydantoin as reacted with 1.17g. (0.003 mol) of 2 B-anilidovinylbenzoxazole ethiodide in the presenceof 0.3 g. of potassium acetate and 5 ml. of acetic anhydride in an oilbath at 135 C. for 7 minutes. To the cooled reaction mixture is thenadded water and crystal formed is filtered, washed with water andalcohol to obtain 1 g. of crude product. By the recrystallization frommethanolpyridine, 0.73 g. of the above compound 3, 1-

acetoxyethyl 5 [(3 ethyl 2(3) benzoxazolylidene)-ethylidene]-3-phenyl-2-thiohydantoin is obtained as red crystal.

Synthesis of compound 5 To 10 ml. of absolute alcohol containing 0.3 g.of triethylamine are added 1.47 g. (0.003 mol) ofZ-B-acetanilidovinyl-6-methoxy-ben1oxazole ethiodide and 0.6 g. (0.003mol) of 1-hydroxyethyl-3-propyl-2-thiohydantoin. The reaction mixture isrefluxed on a water bath for 30 minutes and cooled. The precipitatedcrystal is filtered under suction, washed with alcohol and air dried.The resulting crude product is recrystallized from alcohol to give 0.63g. of the above compound 5, l-hydroxyethyl- 5-[(3-ethyl-6-methoxy 2(3):benzoxazolylidene)-ethy1 idene]-3-propyl-2-thiohydantoin as orange redcrystal.

Synthesis of compound 12 0.54 g. of 1-hydroxyethyl-3-p-chlorophenyl 2thiohydantoin prepared by a procedure similar to that for 1-hydroxyethyl-3-phenyl-2-thiohydantoin and 0.77 g. of 2- 13 anilidovinylbenzoxazole carboxyethylbromide are added to 5 ml. of pyridinecontaining 0.2 g. of piperidine and refluxed for 45 minutes on an oilbath and then cooled. The reaction mixture is neutralized with 15%hydrochloric acid and crystallized. The resulting crystal is filteredand washed with water, alcohol and then ether to give 0.9 g. of crudeproduct. Recrystallization of the crude product fromalcohol-triethylamine and alcoholhydrochloric acid yields 0.6 g. of theabove compound 12, l-hydroxyethyl-S-[(3-carboxyethyl 2(3)benzoxazolylidene) ethylidene]-3-p-ch1orophenyl 2 thiohydantoin as redviolet crystal.

Synthesis of compound 28 0.84 g. (0.002 mol) ofZ-B-anilidovinyl-S-methoxybenzoxazole ethiodide and 0.49 g. (0.002 mol)of 1- cyanoethyl-3-phenyl-2-thiohydantoin are added to 10ml. of pyridinecontaining 0.2 g. of triethylamine and refluxed for 30 minutes on an oilbath. The reaction mixture is cooled and crystallized by adding water.The crystal formed is filtered and washed with alcohol to give 0.83 g.of crude product. By the recrystallization of the crude product frommethanol-pyridine, 0.69 g. of the above compound 28, l-cyanoethyl-5-[(3-etl1yl-5-methoxy2(3 benzoxazolylidene)ethylidene] 3 phenyl 2thiohydantoin is obtained as red crystal. M.P. 242-244 C. A (inmethanol) 501 m Elementary analysis. Found: N=12.80. Calcd.: N: 12.54.

Synthesis of compound 38 1.17 g. of the 2- 3-anilidovinyl-benzoxazoleethyl sulfate and 0.79 g. (0.003 mol) of l-carboxyethyl-3-phenyl-2-thiohydantoin are added to 10 ml. of pyridine containing 0.3 g. oftriethylamine and refluxed for 30 minutes on an oil bath. The reactionmixture is then acidified and cooled to C. Crystal formed is filteredand washed with water, alcohol and ether to give 1.1 g. of crudeproduct. This crude product is purified by dissolving it inalcohol-triethyl-amine solvent and acidifying it with dilutedhydrochloric acid to crystallize and thus 0.65 g. of pure compound 38,l-carboxyethyl 5 [(3-ethyl-2(3)- benzoxazolylidene)ethylidene] 3 phenyl2 thiohydantoin is obtained. M.P. 277-279 C. A (in methanol) 495 mn.

Elementary analysis. Found: N=9.74. Calcd.: N=9.64.

Synthesis of compound 52 1.17 g. (0.003 mol) of2-[3-anilidovinyl-benzoxazole ethyl sulfate and 0.62 g. (0.003 mol) ofl-carb-amoylethyl-3-n-propyl-2-thiohydantoin are refluxed for 30 minuteson an oil bath together with 15 ml. of pyridine containing 0.3 g. oftriethylamine. Thereafter, the reaction mixture is cooled and crystalformed is filtered, washed with ether and dried to yield 0.9 g. of crudeproduct. By the recrystallization from methanol-pyridine, 0.55 g. of theabove compound 52, 1-carbamoylethyl-5-[(3-ethyl-2(3)-benzoxazolylidene)ethylidene]-3-n-propyl 2 thiohydantoin isobtained as red needle crystal. M.P. 279- 282 C. 1 (in methanol) 486 mu.

Elementary analysis. Found: N=14.0l. N=13.99.

The new polymethine merocyanine dye used in this invention is preferablyadded to photographic emulsion in an amount of 01-10 mg. per 100 g. ofsilver halide emulsion. However, this range is not critical and agreater or smaller amount may be used. As solvents, those ordinarilyused such as methanol, ethanol, dimethyl sulfoxide Calcd.:

and the like can be used. Addition of the dye to photographic emulsionmay be made at any stage before, during or after the second ripening andpreferably immediately after the second ripening. It is to be noted thatuse of the polymethine merocyanine dyeaccording to this invention doesnot cause any adverse effect on photographic emulsion which ischemically sensitized by the noble metal-, sulfur-, reductionandpolyalkylene oxide-sensitizations and moreover by the supersensitizationaccording to the method known per se. Further, the dye of the inventionis applicable also to photographic emulsion containing an anionicwetting agent (surface active agent).

Emulsion sensitized with the new cyamine dye of this invention is coatedon a support such as cellulose acetate, polyester film and baryta paperand dried to produce a light sensitive silver halide photographicmaterial.

The new polymethine merocyanine dye used in this invention is applicableto ordinary (black-and-white) photographic emulsion as well as tomulti-layer color photographic emulsion. Moreover, the polymethinemerocyanine dye does not cause any interaction with a color formercontained in the emulsion and not diffuse into an adjacent layer of thesensitive material. By using the new dye, color staining afterdevelopment is avoided and desirable sensitization affecting no adverseeffect on photographic characteristics can be attained.

The present invention is illustrated by the following examples.

EXAMPLE 1 A high-speed silver bromoiodide photographic emulsioncontaining 3 mol percent of silver iodide was. prepared according to aneutral process. Immediately after the second ripening of the saidemulsion, 100 g. each of the emulsion was added with 0.5 to 5 cc. of amethanolic solution containing 0.05% by Weight of the compound specifiedin Table 1. Each of the thus resulted emulsions was coated on film basesand then dried under the same conditions.

Each of the light-sensitive photographic films as prepared above wasexposed to light according to a JIS method (K 7609) and then treatedwith an NSG developer at 20 C. for 5 minutes. The said NSG developer hasthe following composition:

G. Monomethyl p-aminophenol sulfate 3 Sodium sulfate (anhydrous) 50Hydroquinone 6 Sodium carbonate (monohydrate) 30 Potassium bromide 1Water to make up to 2 litre.

The storageability of the developed films was determined by measuringphotographic speed according to a 115 method (K 7609) after storage forcertain period. Measurement of spectral sensibility was made by using adiffraction lattice type spectrophotometer (with a light source of 2848K.) manufactured by Shimazu Mfg. Co., Ltd., Japan. The photographicproperties and residual color density are set forth in Table 1, whereinphoto- TAB LE 1 7 Incubated at 55 C. Ineubated at 50 C. and

Immediately after preparation for 3 days after the RH. for 3 days of theemulsion preparation after the preparation Amount Relative speed Sensl-Relative speed Relative speed use tlzation Residual (oo./g. White Greenmax. White Green White Green color 7 emulsion) light light Fog (mu)light light Fog light light Fog density Compound N 0.:

(1) 2 100 115 0. 03 545 115 0. 03 105 0. 03 0. 03 2 105 130 0. 02 545110 135 0. 03 100 130 0. 02 0. 02 2 110 140 0. 02 550 110 140 0. 03 105135 0. 02 0. 02 2 105 120 0. 02 545 125 0. 03 110 125 0. 03 0. 04 1 108110 0. 03 545 110 0. 04 110 110 0. 03 0. 03 2 107 0. 04 550 108 125 0.05 105 120 0. 04 0. 06 2 105 120 0. 03 545 105 120 0. 03 105 120 0. 030. 03 5 112 145 0. 04 545 110 145 0. 05 110 0. 04 0. 03 2 100 105 0. 03545 102 110 0. 04 100 105 0. 03 0. 03 (52) 3 105 120 0. 03 540 105 1150. 04 103 110 0. 03 0. 04 Control 2 100 100 0. 03 550 105 103 0. 05 9894 0. 03 0. 06

13 graphic speed is expressed as a relative value in comparison with aphotographic speed of a control film containing the optimum amount of1-ethyl-5[3-methyl-2(3)- benzoxazolylideneethylidene]-3-pheny1-2-thiohydantoin, the speed of said control filgnbeing rated as 100.

14 to a MS method (K 7609) and treated with a color developer in a usualmanner. After bleaching and fixing, the film was subjected tosensitometry to determine photographic speed and fog. The test resultsare set forth in 5 Table 3.

TABLE 3 Immediately after Incubated at 40 C. for preparation of the 3hrs. after the emulsion preparation Amount Relative speed Relative speedSensitiused zation Compound (ec./l g. White Green White Green maximum No. emulsion) light light Fog light light Fog (me) As apparent from theabove table, the light-sensitive photographic materials of the inventionare safe from fogging and dye staining and they are excellent inphotographic sensitivity.

In FIG. 1 and FIG. 3, the spectral sensibility curves of the emulsionsadded with the compound 6 and the com pound 40, respectively, are shownby solid lines. In these figures, the spectral sensibility curves of thecontrol emulsion are indicated by dotted lines.

EXAMPLE 2 100 g. each of a low speed light-sensitive silverchlorobromide photographic-positive emulsion was added with an optimumamount (0.5- cc.) of a methanolic solution containing 0.05% by weight ofthe compound specified in Table 2. The emulsion was coated on a filmbase and then dried. The thus obtained light-sensitive film wassubjected to sensitometry. The test results are set forth in Table 2.

As apparent from the above table, the light-sensitive photographicmaterials of the present invention are safe from fogging and colorstaining and excellent in photographic sensitivity.

The spectral sensibility curves of the emulsions added with the compound12 and the compound 39 are shown by solid lines, in FIG. 2 and FIG. 4,respectively. In

these figures, the spectral curves of the control emulsion are indicatedby dotted lines.

EXAMPLE 3 100 g. of the high-speed light-sensitive silver bromoiodideemulsion used in Example 1 was added with up to 5 cc. of a methanolicsolution containing 0.05% by weight of the compound specified in Table3. Into the resulting emulsion,1-(4-phenoxy-3-sulfophenyl)-3-heptadecyl-5-pyrazolone as a color formerwas dispersed. The dispersion was adjusted at pH 6.8. Immediatelythereafter or after incubation at 40 C. for 3 hours, the green-sensitivecolor-photographic emulsion th-us prepared was coated on a film base andthen dried. The light-sensitive color-photographic film was exposed tolight according It is apparent from the above data that thelight-sensitive photographic materials of the invention are safe fromfogging and are well sensitized through an interaction of a sensitizingdye with a color former.

What we claim is:

1. A light-sensitive silver halide photographic material characterizedby containing, as an ingredient for its photographic emulsion layer, asensitizing dye of the general formula:

wherein R is an alkyl group, a carboxy alkyl group or a sulfo alkylgroup; R is hydroxy, cyano, alkoxy, carboxy, acyloxy or carbamoyl; n isan integer of 2 to 3; R is an alkyl, aryl, alkenyl or aralkyl; and Zmeans an atomic grouping capable of forming, together with the adjacentnitrogen and carbon atoms, a benzoxazole ring, a naphthooxazole ring, athiazole ring, an indolenine ring or a quinoline ring.

2. The light-sensitive silver halide photographic material as claimed inclaim 1; said photographic emulsion layer further comprising a memberselected from the group consisting of sulfur-, gold-, polyoxyalkyleneandreductive sensitizers.

3. The light-sensitive silver halide photographic material as claimed inclaim 1; said photographic emulsion layer further comprising a colorformer.

4. The light-sensitive silver halide photographic material as claimed inclaim 3 wherein said color former is a magenta coupler having anindazolone or pyrazolone nucleus.

5. The light-sensitive silver halide photographic material as claimed inclaim 1, said photographic emulsion layer further comprising1-hydroxyethyl-5-[(3-sulfopropy1-2-(3) benzoxazolylidene)-ethylidene] 3phenyl- Z-thiohydantoin pip'eridinium salt or l-carboxyethyl-S- [(3ethyl 2(3) benzoxazolylidene)-ethylidene] 3- phenyl-Z-thiohydantoin.

References Cited UNITED STATES PATENTS 2,493,748 1/1950' Brooker et al.9610'2 2,497,876 2/1950 Fallesen et a1 96-102 2,828,203 3/1958MacWilliam 96l02 J. TRAVIS BROWN, Primary Examiner US. Cl. X.R.

